FM 2015 Adrian Beard

SCI Fire and
Materials Group
OVERVIEW OF NON-
HALOGEN FLAME
RETARDANTS
Public
Dr. Adrian Beard

Clariant Flame Retardants
pinfa.org
05.11.2015
2 Public, Overview of non-halogenated flame retardants
Dr. Adrian Beard, Clariant Flame Retardants, pinfa.org, 05.11.2015
Global Consumption of Flame Retardants (2013)
5622 Mio USD FR Market by Region 2.1 mio. MT FR Market by Chemistry

Share in percent, 2013 Share in percent, 2013
Others
Other Asia North America 12%
Brominated
18% Antimony 12% 17%
20% 7%
Oxides
7%
Central and
2% South America
16%
Organo-
0%
China 1% phosphorus
27% 2% 20%
Western Europe
34% 14%
10% Alumina-
Central and
Trihydrate Chlorinated
Japan AfricaEastern Europe
Middle East
Estimated average growth 2013 to 2018 ca. 3.4% p.a.

Source: SRI/IHS consulting 2014
The Combustion Process

Phosphorus FRs - mechanism
• elemental (red)
phosphorus, inorganic
and organic phosphorus
compounds are used
• main mechanism is by
formation of a char layer
at the surface, stopping
the contact between fuel
and air
• generally less smoke,
because no forced
incomplete combustion,
less acidic gases
Phosphorus based Flame Retardants - examples
_
O
R1
P O M n+
R2
n
Polyphosphonate phosphinic acid salts
Inorganic hydroxide FRs - mechanism
• aluminium and
magnesium hydroxides
are the most common
• water is released upon
heating, leading to a
cooling of the
combustion zone
• physical effect is less
efficient  high
amounts are necessary
• less smoke, because
no forced incomplete
combustion, no acidic
gases
Nitrogen and Inorganic Flame Retardants - examples

REACH is steaming ahead in Europe
1 - 10 t
> 1000 t
Set-up > 100 t N: R50-53 100 - 1000 t 10 - 100 t
of the > 1 t CMR
Agency Pre-registration:
1-June to 30-Nov 2008
June June Nov June June

2007 2008 2010 2013 2018
Most flame retardants are already registered –

dossiers are available on ECHA website:
http://echa.europa.eu/web/guest/information-on-chemicals/registered-substances
REACH and Flame Retardants

• Annex 17 Restrictions lists these FRs: Deca-BDE: Norway has
• Pentabromodiphenyl ether* (PentaBDE, 0,1% w/w) submitted a proposal to
add the commercial
• Octabromodiphenyl ether* (OctaBDE, 0,1% w/w) mixture (c-decaBDE) to
• Not allowed in articles for skin contact (e.g. textiles): the Stockholm Convention
on Persistent Organic
• Tris(aziridinyl)phosphinoxide Pollutants  ECHA to
• Tris (2,3 dibromopropyl) phosphate (TRIS) prepare Annex XV dossier
• Polybromobiphenyls (PBB)
• Annex 14 (Candidate) List of Substances of Very
High Concern for Authorisation:
• Hexabromocyclododecane (HBCD) – PBT substance
• Tris(chloroethyl)phosphate (TCEP) – Reprotox Cat. 1b
• Alkanes, C10-13, chloro (Short Chain Chlorinated Paraffins) - PBT and vPvB
• Boric Acid – Reprotox
• Trixylylphosphate (TXP) – Reprotox Cat. 1b
* as commercial formulations, i.e. including other congeners
Europe RoHS and WEEE
• EU Directive on the Restriction Of Hazardous Substances in electric and electronic

equipment (RoHS, 2002/95/EC) was published in 2003
• Bans the heavy metals Cd, Pb, Cr (VI), Hg as well as PBBs and PBDEs, in E&E
equipment since July 2006 (with exemptions for certain applications and duration)
• Directive “recast” in 2011 and published as 2011/65/EU
• no new substance bans (Annex II), but to be
reviewed by 2014-07 (Art. 6): certain phthalates
restricted by EU/2015/863
• Restricted substances to be updated regularly; project
by Austrian Umweltbundesamt produced priority list
and methodology
• WEEE Directive recast as 2012/19/EU
• Higher recycling quotas and additional product
groups covered picture: CT/tsa medien
US-EPA: New Focus on Alternatives

Assessment to BFRs
• Evaluation of environmental and health properties
of alternatives to:
• Tetrabromo bisphenol-A
• Penta- and Decabromo diphenylether
• Hexabromo cyclododecane
• Hazard focused approach
• Suitable alternatives to problematic products were
identified
• No black and white picture:
• Alternatives (incl. halogen free) have chemical
hazards, too, however,
• Need to check relevance, e.g. by GreenScreen
• Data gaps filled by read-across, computational
methods or expert judgement
www.epa.gov/dfe
GreenScreen
• Assessment scheme with

4 rating levels = “scores”
• pinfa has run a pilot project
to have some flame retardants
evaluated
• Quick and simplified approach,
however, the devil is in the detail - like
data gaps, ambiguous and contradictory
data; review process; narrow
classification boundaries
• http://www.cleanproduction.org/
ENFIRO: Life Cycle Assessment of
Environmentally Compatible Flame
Retardants
Impact Prioritization
assessment and selection
Chemical
alternative
Hazard
Exposure cycle
Risk
Fire &
assessment
Application
performance
The following slides are
quoted from an ENFIRO
presentation, courtesy of
Pim Leonards, project
coordinator
Evaluation of HFFRs reveals many FRs with
good environmental and health profile
Generally safe, • Aluminium diethylphosphinate (Alpi) • Inorganic and organic
substances with low acute
few issues of • Aluminium hydroxide (ATH) (eco-)toxicity and no
low concern • Ammonium polyphosphate (APP) bioaccumulation potential
identified • Melamine polyphosphate (MPP) • Chemical stability required for
application results in limited
• Dihydrooxaphosphaphenanthrene (DOPO) degradation (persistence)
• Zinc stannate (ZS) • Stannates: in vitro (neuro-)tox
• Zinc hydroxstannate (ZHS) effects were not confirmed in-
vivo, probably due to low
bioavailabillity
Low level of • Resorcinol bisphosphate (RDP) • RDP toxicity to aquatic

organisms is main concern, may
concern for • Bisphenol-A bisphosphate (BDP) be linked to impurities (TPP).
potential Low and high toxicity are found
environmental for same test species, which is
may be due to batch differences
and health • BDP is persistent
impact
Some issues of • Triphenyl phosphate (TPP) • Toxicity of TPP to aquatic
organisms is main concern,
concern, risk • Nanoclay potential endocrine effects
assessment • Nanoclay showed strong in
necessary vitro neurotoxicity. May be due
to the nanoparticle coating
Public, Overview of non- 18

Assessment of FR/polymer material
Leaching FR
to air
(off-gassing)
Leaching FR FR+polymer Fire

to water performance
(concentrations and (e.g. Toxic gasses)
toxicity)
Applications
19
Fire Performance BFRs - HFFRS
10000
Fire Growth PBT
PBT+
1000
Alpi
PBT+
BPS
PBT+Alpi+
nanoclay
100
0.04 0.05 0.06 0.07 0.08 0.09 0.10 0.11 0.12
Smoke production (g/g)
Zoomed
view
•In general, HFFRs had improved smoke suppression
•HFFRs had similar fire performance characteristics as
BFRs in polymers, except for polymer blends
Application performance
• All formulations (HFFR and BFR) showed equal or better

performance for processability for injection moulding
• Important input was received from the Stakeholder forum
• Printed circuit boards (PCBs) with HFFRs where as good
as or better compared to the reference PCBs produced
using BFRs
Viable alternatives are available
FR Material Product
Hazard Technological Impact assessment

assessment studies
• Some HFFRs are • HFFRs produce • Improper treatment
less toxic than BFRs less smoke, except of products with
• Suitable alternatives: RDP, BDP BFRs can produce
• Alpi, DOPO, APP, • HFFRs leach as dioxins
MPP, ATH, ZHS, ZS much as BFRs • HFFRs will not
• Leaching is polymer produce dioxins
dependent
Market Drivers: NGOs, Ecolabels, Green

Public Procurement
• Many ecolabels have
restrictions for flame
retardants
• Often detailed
information on the flame
retardants which are
used is required
• EPEAT 2012: mandatory
and optional require-
ments for halogen-free
plastics
• EU Ecolabels: task force
on chemicals to revise
simple hazard approach
pinfa EU Members in 2015
www.pinfa.org 27
Who is pinfa?
• pinfa was established in 2009 as a Sector Group within Cefic, the European
Chemical Industry Council
• pinfa North America was founded in 2012
• pinfa, the Phosphorus, Inorganic and Nitrogen Flame Retardants
Association represents manufacturers and users of the three major
technologies of non-halogenated flame retardants.
• pinfa members share the vision of continuously improving the
environmental and health profile of their flame retardant products and
offering innovative solutions for sustainable fire safety.
• Part of the mission of pinfa is to provide information on non-halogenated
phosphorus, inorganic and nitrogen flame retardants
www.pinfa.org 29
pinfa product selector
• List of more than 33 flame

retardants
• Information on applications and
regulatory status
• Applications range from
- Thermoplastics
- Foams
- Textiles
- Paints/Coatings
- Adhesives
- Thermosets
- Wire and cables
• Actual REACH status for products
is currently being implemented
• www.pinfa.org
www.pinfa.org 30
Further Reading - brochures
• E&E applications
• Transportation
• Building &
Construction
• Explain flame
retardants by
application
• www.pinfa.eu/library
/brochures.html
www.pinfa.org 31
Requirements on Flame Retardants
Compatibility with the

polymer and processing
Ecology and
Cost Flame Retardant
Toxicology
Flammability
www.pinfa.org 32
Summary
• The scientific and public debate on flame

retardants has led to some regulatory restrictions
on mostly halogenated flame retardants (e.g. RoHS
and WEEE directives, REACH in Europe) as well as
the evaluation of alternatives.
• The EU ENFIRO project confirmed that
• viable alternative flame retardants are available,
HFFRs have similar fire performance and
Picture: R. Baumgarten / Clariant
technical application capabilities as BFRs
• In general, halogen free systems produce less
smoke and less toxic components in smoke
• Flame retardants manufacturers in pinfa try to
develop new and better products as well as supply
their customers with all necessary information.
Thank you
FOR YOUR ATTENTION

FM 2015 Adrian Beard

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FM 2015 Adrian Beard

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SCI Fire and

Dr. Adrian Beard

Global Consumption of Flame Retardants (2013)

5622 Mio USD FR Market by Region 2.1 mio. MT FR Market by Chemistry

Estimated average growth 2013 to 2018 ca. 3.4% p.a.

The Combustion Process

Phosphorus FRs - mechanism

Phosphorus based Flame Retardants - examples

Inorganic hydroxide FRs - mechanism

Nitrogen and Inorganic Flame Retardants - examples

REACH is steaming ahead in Europe

June June Nov June June

Most flame retardants are already registered –

REACH and Flame Retardants

Europe RoHS and WEEE

• EU Directive on the Restriction Of Hazardous Substances in electric and electronic

US-EPA: New Focus on Alternatives

• Assessment scheme with

Low level of • Resorcinol bisphosphate (RDP) • RDP toxicity to aquatic

Public, Overview of non- 18

Leaching FR FR+polymer Fire

Fire Growth PBT

• All formulations (HFFR and BFR) showed equal or better

Hazard Technological Impact assessment

Market Drivers: NGOs, Ecolabels, Green

• List of more than 33 flame

Compatibility with the

• The scientific and public debate on flame

FOR YOUR ATTENTION

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